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O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
Journal Name
ARTICLE
H); 13C NMR (126 MHz; CDCl
010, 132, 18199–18205.
(a) J.-B. Xia, C. Zhu and C. Chen, J. Am. Chem. Soc., 2013, 135,
7494–17500; (b) P. Xu, S. Guo, L. Wang and P. Tang, Angew.
1
2
1
(
8
3
; SiMe
4
): 24.0, 49.0, 112.8 (t, JCF
=
2
DOI: 10.1039/C9OB00540D
34 Hz), 120.9, 121.5, 126.2, 126.7, 134.5 (t, JCF = 23 Hz), 137.8,
7
8
1
9
3 6 6
47.1 (t, JCF = 9 Hz), 153.5; F NMR (470 MHz, CDCl ; C F ): 47.2
1
dd, JFH = 55, 3 Hz); IR (neat): 2962, 2925, 2856, 1469, 1375, 1022,
Chem., Int. Ed., 2014, 53, 5955–5958; (c) G. Yuan, F. Wang,
N. A. Stephenson, L. Wang, B. H. Rotstein, N. Vasdev, P. Tang
and S. H. Liang, Chem. Commun., 2017, 53, 126–129.
–1
+
12 2
18, 771 cm ; HRMS (EI): m/z calcd. for C12H F [M] : 194.0907;
Found: 194.0905.
(a) P. S. Fier and J. F. Hartwig, J. Am. Chem. Soc., 2012, 134,
1
-Difluoromethylidene-2-di(ethoxycarbonyl)methyl-1,2,3,4-
5
524–5527; (b) G. K. S. Prakash, S. K. Ganesh, J.-P. Jones, A.
1
tetrahydronaphthalene (5): H NMR (500 MHz; CDCl
3 4
; SiMe ):
Kulkarni, K. Masood, J. K. Swabeck and G. A. Olah, Angew.
Chem., Int. Ed., 2012, 51, 12090–12094; (c) X.-L. Jiang, Z.-H.
Chen, X.-H. Xu and F.-L. Qing, Org. Chem. Front., 2014, 1,
1
2
1
7
7
.22 (t, J = 7.1 Hz, 3H), 1.25 (t, J = 7.1 Hz, 3H), 1.97–2.09 (m, 2H),
.81 (ddd, J = 17.7, 5.9, 3.8 Hz, 1H), 2.88 (ddd, J = 17.7, 10.7, 6.9 Hz,
H), 3.43 (d, J = 11.1 Hz, 1H), 3.61–3.67 (m, 1H), 4.13 (dq, J = 10.9,
.1 Hz, 1H), 4.17 (dq, J = 10.9, 7.1 Hz, 1H), 4.20 (q, J = 7.1 Hz, 2H),
.11–7.15 (m, 1H), 7.18 (dd, J = 3.5, 3.5 Hz, 1H), 7.19 (dd, J = 3.5, 3.5
7
2
74–776; (d) Y. Gu, X. Leng and Q. Shen, Nat. Commun.,
014, 5, 5405–5411; (e) K. Aikawa, H. Serizawa, K. Ishii and K.
Mikami, Org. Lett., 2016, 18, 3690–3693; (f) L. Xu and D. A.
Vicic, J. Am. Chem. Soc., 2016, 138, 2536–2539; (g) H.
Serizawa, K. Ishii, K. Aikawa and K. Mikami, Org. Lett., 2016,
1
3
Hz, 1H), 7.43 (ddd, J = 5.7, 3.5, 3.5 Hz, 1H); C NMR (126 MHz;
CDCl ; SiMe ): 13.9, 14.0, 25.1, 25.3, 32.7, 52.9, 61.4, 61.5, 90.0
dd, JCF = 22, 11 Hz), 126.3, 127.2, 127.4 (dd, JCF = 4, 4 Hz), 128.0,
1
8, 3686–3689; (h) C. Lu, H. Lu, J. Wu, H. C. Shen, T. Hu, Y. Gu
3
4
and Q. Shen, J. Org. Chem., 2018, 83, 1077–1083; (i) C. Xu,
W.-H. Guo, X. He, Y.-L. Guo, X.-Y. Zhang and X. Zhang, Nat.
Commun., 2018, 9, 1–10.
(
1
(
1
28.1, 129.0, 135.49, 135.53, 152.9 (dd, JCF = 293, 286 Hz); 19F NMR
; C ): 73.5 (d, J = 36 Hz, 1F), 76.8 (d, J = 36 Hz,
470 MHz, CDCl
3
F
6 6
9
(a) Z. Feng, Q.-Q. Min and X. Zhang, Org. Lett., 2016, 18, 44–
47; (b) X.-Y. Deng, J.-H. Lin and J.-C. Xiao, Org. Lett. 2016, 18,
4384–4387; (c) Z. Feng, Q.-Q. Min, X.-P. Fu, L. An and X.
Zhang, Nat. Chem., 2017, 9, 918–923; (d) W. Miao, Y. Zhao,
C. Ni, B. Gao, W. Zhang and J. Hu, J. Am. Chem. Soc., 2018,
–
1
F); IR (neat): 2981, 2937, 1755, 1728, 1240, 1032, 766 cm ;
HRMS (EI): m/z calcd. for C18
38.1325.
+
20
H F
2
O
4
[M] : 338.1330; Found:
3
1
40, 880–883; (e) J. Sheng, H.-Q. Ni, K.-J. Bian, Y. Li, Y.-N.
Wang and X.-S. Wang, Org. Chem. Front., 2018, 5, 606–610.
10 For the two-step syntheses of (difluoromethyl)arenes, see:
a) K. Fujikawa, Y. Fujioka, A. Kobayashi and H. Amii, Org.
Conflicts of interest
There are no conflicts to declare.
(
Lett., 2011, 13, 5560–5563; (b) Y.-M. Su, Y. Hou, F. Yin, Y.-M.
Xu, Y. Li, X. Zheng and X.-S. Wang, Org. Lett., 2014, 16, 2958–
2
961; (c) H. Shi, A. Braun, L. Wang, S. H. Liang, N. Vasdev and
Notes and references
T. Ritter, Angew. Chem., Int. Ed., 2016, 55, 10786–10790.
1
1
1 For reviews, see: (a) W. R. Dolbier, Jr., Acc. Chem. Res., 1991,
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(a) B. E. Smart, Organofluorine Chemistry, Principles and
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2 (a) K. Fuchibe, Y. Mayumi, N. Zhao, S. Watanabe, M. Yokota
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828; (b) K. Fuchibe, Y. Mayumi, M. Yokota, H. Aihara and J.
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For a review on bioisosteres in drug design, see: N. A.
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359–2363; (d) K. Fuchibe, K. Shigeno, N. Zhao, H. Aihara, R.
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961, 2, 43–49; (b) A. E. Lloyd, P. L. Coe, R. T. Walker and O.
1
1
3 For C–C bond formation of 1,1-difluoroallenes at the position
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Houlton, W. B. Motherwell, B. C. Ross, M. J. Tozer, D. J.
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4 For hydrometallation and hydrosilylation of 1,1-
difluoroallenes with a stoichiometric amount of metal
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106; (d) J. A. Erickson and J. I. McLoughlin, J. Org. Chem.,
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Med. Chem., 2009, 52, 1525–1529; (f) H. Knust, G.
Achermann, T. Ballard, B. Buettelmann, R. Gasser, H. Fischer,
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4
5
For synthetic utility of the difluoromethyl group, see: J. B.
Geri, M. M. Wade Wolfe and N. K. Szymczak, J. Am. Chem.
Soc., 2018, 140, 9404–9408.
For reviews, see: (a) T. Liang, C. N. Neumann and T. Ritter,
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5 (a) K. Fuchibe, T. Morikawa, K. Shigeno, T. Fujita and J.
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6 K. Fuchibe, M. Ueda, M. Yokota and J. Ichikawa, Chem. Lett.,
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7 For a review on synthetic utility of 1,1-difluoroalkenes, see: X.
6
(a) C.-L. J. Wang, Org. React., 1985, 34, 319–400; (b) R. P.
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